Diazotype compositions containing ethylene oxide derivatives of amino diazos



Patented Oct. 31, 1950 UNITED STATES PATENT OFFICE DIAZOTYPE COMPOSITIONS CONTAINING ETHYLENE OXIDE DERIVATIVES OF AMINO DIAZOS William H. -yon Glahn, Loudonville, Lester N. Stanley, Delmar, and George T. Parker, Albany, N. Y., assignors to General Aniline & Film Corporation, New York, N. Y., a corporation of Delaware No Drawing. Application October 12, 1946, Serial No. 702,880

4 Claims.

This invention relates to the production of diazotype light-sensitive layers or other diazo-type materials and more particularly to diazotype materials wherein the light-sensitive agent is a diazo derivative of an aromatic ortho or para diamine having one of the following formulas:

wherein n is any integer greater than 1 and n is any integer; R is a member of the group consisting of alkyl, hydroxyalkyl, alkoxyalkyl, aryl, aralkyl and acyl; X is a member of the group consisting of hydrogen, aliphatic, aromatic, heterocyclic' and acyl such as acetyl, benzoyl and furoyl andAr is an aromatic radical containing no alkyl substituents of greater than 3 carbon atoms content. The aromatic nuclei may be otherwise substituted by such common substituen-ts as halogen, C1 to C3 alkyl, alkoxy, hydroxyalkyl, carboxy, carboalkoxy and sulfo groups.- i

. It has been found that diazo compounds of this class when developed with one of the azo components generally employed for diazotype work, either by the .dryydevelopment process wherein the azo component and diazo compound are both contained in thelight-sensitive layer or by the wet development process where'only the diazo fcompound is contained in the light-sensitive layer and the azo component isgapplied as part of an alkaline developing solution, reproductions can be obtained having images of brightdark tones on a clear white background wherein the images are washfast and possess great permanency. These diazos also possess good stability when used in a two-component system together with the azo component for the dry developing diazotype process and are particularly characterized by their excellent printing speed in either a two-component or one-component system.

When used in conjunction with the proper azo components suchlas resorcinol and resorcinol derivatives, these diazps will reproduce the image in the sepia shade which has excellent photographic density or opacity to ultraviolet light. Accordingly, when used in such a combination the diazos of this class i are eminently suited for transition printing where a transparent or semitransparent intermediate" diazotype print is made 2 i for the purpose of using such intermediate print as an original in making further copies.

Although this invention embraces all diazo derivatives of the aromatic ortho and para diamines of the foregoing class, a preferred group of such diazos which is particularly suitable for two-component diazotype compositions comprises the diazo compounds derived from substitutedpphenylene diamines having the following formu las:

cleus may be further substituted as indicated above but when substituted by alkyl, such alkyl 7 R and substituent should not contain more than three carbon atoms. The invention will be particular-,-

ly described with reference to this preferred class,

of diazo derivatives but it is understood that such description is exemplary of the class of ortho and para aromatic diamines wherein the phenylene nucleus of this preferred class may be substituted by naphthalene, anthracene or other aromatic nuclei, wherein the diazotized amino group and the substituted amino group may bear either an. ortho or para relationship to each other on the aromatic nucleus and whereinthe terminal hydroxy group and the polyethylene oxide members of the substituted aminogroup may be substituted as indicated in the general formula.

In producing the diazotype materials from coat ing solutions containing the diazo compounds of this invention as the light-sensitive agents, the. base or support carrying orlcontaining the lightsensitive compounds, the azo components and other coating materials is coated, dipped, brushed or sprayed with the sensitizing solution bymeans; well known to the art, the particular typeof apblication depending upon the carrier employed. As] carriers, such materials as paper or cloth which may be opaque, semi-transparent or of' a transparenti'zed type; film such as prepared from cellulose nitrate, cellulose acetate or other cellulose esters or regenerated cellulose; glass plates or sheet metal may be employed. Where paper is used as the base or support for the light-sensitive coating, the coating solution is generally applied by using a trough and doctor blade but may, if desired, be brushed on or sprayed. When a film is used as a support, swelling agents should be added to the coating solution in order to obtain proper penetration and the solution is generally applied bya dipping method. In addition to the diazo compound, azo component and such swelling agents as may be added, the coating solution may contain the usual adjuvants such as metal salts designed to intensify the dye images, aluminum Sulfata'titanium ammonium fluoride, nickel sulfate and the like for increasing water proofing qualities; stabilizing agents such as thiourea, thiosinamine, naphthalene trisulfonic acid and the like; acids designed to retard precoupling such as citric acid, tartaric acid, boric acid and the like; and hygroscopic agents such as glycol, glycerine, dextrin and the like. As coupling components we may use any azo coupling component known to be suitable for diazotype light-sensitive layers. As suitable azo components, there may be mentioned 2,3-dihydroxy naphthalene and its sulfonic acid derivatives, phloroglucin, naphthalene guanidines such as 7-hydroxy naphthalene-l-guanidine and 5-hydroxy naphthalene-1-biguanidine; acetoacetic acid amides such as acetoacetic acid cyclohexyl amide, acetoacetic acid benzylamide and acetoacetic acid-a-amino pyridine; substituted naphthols such as lmethy1-wdimethylamino-2-hydroxy naphthalene, 2.6 dimethy1-8-hydroxy naph-. thalene and its reaction product with formaldehyde dimethylamine; hydroxynaphtho imidazoles such as 7hydroxy naphtho-1',2:4,5 imida ole and 2 carboxyethyl 7 hydroxynaphtho- 1'2 ;4,5-imidazole; phenol and phenol. derivatives, cresols, resorcinol and resorcinol derivatives such as 4-chlororesorcinol and dichlororesorcinol and resorcinol esters and ethers. Some of these azo components, notably those of the resorcinol family which will produce sepia images, have a fast coupling rate. This tends to impair the precoupling stability of a two-component system containing such an azo component. Since it is desirable to use these azo components which will produce sepia shades in the production of diazotype transparencies, precoupling instability is a decided disadvantage as precoupling instability Will produce background color in the transparency, which background color will absorb actinic light in areas where the transparencies should transmit the light. This disadvantage is overcome when using the diazos of this invention since the diazos of the aromatic ortho and para diamines having the polyethylene oxide substitutions on the undiazotized amino group have a high degree of resistance to precoupling even in combinations cotntaining azo components having a fast coupling ra e.

The diazo compounds may be applied to the support either from a solution containing the diazo compound as the only dye component or from a solution containing both the diazo compound and the azo component. Where the coating solution contains no azo component, precoupling stability is, of course, no problem. However, such factors as printing speed and ability to produce images having good wash fastness, good photographic resolution and shades of good photographic density as well as visual density are just as important in evaluating the efiiciency of such a single component process as they are in the case of the two-component process where the azo component. is also contained in the coating solution. In the single component process, the azo component is added to the developing solution which is applied by a contact or fog spray method to the exposed diazotype layer in order to produce the dye image.

The following examples will serve to illustrate further the preparation of diazotype photoprinting materials from the diazo compounds of our invention, it being understood that the invention is not limited to the particular materials or proportions therein described. Unless otherwise specified, the parts are by weight.

Example 1 Paper is coated in the usual manner with a solution containing per cc. of water:

2.5 g. N ,N-di(hydroxyethoxyethyl) aniline p-diazo ZnClz double salt 1.7 g. 2,3 dihydroxynaphthalene-6-sulfonic acid 8.0 g. citric acid 4.0 g. thiourea Example 2 A paper support is coated in the usual manner with a solution containing per 100 cc. of Water:

p-diazo ZnClz double salt 1.1 g. 2,3 dihydroxynaphthalene 8.0 g. citric acid 4.0 g. thiourea After exposing this coating'vvhich has been dried under a pattern the image is developed'by drawing through ammonia fumes to a bright blue on a clear white background. The printing speed during exposure is excellent and the coated paper has very good storage stability when tested either under average storage conditions over a period of time or by accelerated aging tests.

Example 3 Transparentized paper is coated in the usual manner with a solution containing per 100 cccof water:

p-diazo ZnCl2 double salt 2.5 g. resorcinol 8.0 g. citricacid 4.0 g. thiourea After drying the thus coated transparentized paper, it is exposed to light under a pattern and the image developed by drawing it through ammonia fumes. The resulting image of the original pattern is in a sepia shade on a clear transparent background. This sepia image has good photographic density as well as visual density and thus is eminently suited for use as an intermediate transparency in the production i u t P The coated transparentized N,l T-di (hydroxyethoxyethyl) aniline N,N-di(hydroxyethoxyethyl) aniline paper priorfto' exposure and development has" good storage stability thus eliminating any background color in the transparency or the final copy due to premature coupling of the dye com- The diazo compound employed in Examples 1, 2 and 3 may be replaced by the following diazo compounds of the class contemplated by this invention with similar results. Thus by substituting any one of the following diazos for the ponents during storage. v 5

The diazo compound employed in these exam- N,N di(hydroxyethoxyethyl)aniline p diazo ples may be'prepared by the autoclave reaction ZnClz double salt of Examples 1 vand 2, bright of 2 mols of ethylene oxide at 90 C. on 1 mol of blue images on a white background may be ob- N,'N-dihydroxyethyl aniline or the reaction of 4 tained from a coating which has good printing mols of ethylene oxide upon 1 mol of aniline. 10 speed and good storage stability and by making The resultingbase is nitrosated or nitrated in the same substitutions in Example 3, sepia colthe usual manner. The nitroso or nitro group is ored images having good opacity to ultraviolet then reduced by zinc dust and H01 and the thus light or good photographic density in the dye obtained amine is diazotized in the usual manner areas may be obtained from coatings which have to give the zinc chloride double salt. 15 good printing speed and good storage stability.

Diazo Compound ProbableFormula Preparation N,N-di-hydroxyethyl ani- 01120112011 Prepared by autoclave reaction of 2 mols of ethylene oxide at 90 line-p-diazo' ZnClz dou- O with 1 mol of aniline followed by nitrosation or nitration, L ble salt. 1 N reduction of the nitroso or nitro group and diazotization of the amino group. 01120112011 N-(hyrlroxydiethoxyethyl) }0 H40) 311 N (hydroxyethoxyethyl) aniline p diazo N Z1101; double salt; \(0 H O) H N,N-di (hydroxytriethoxy- )0 H4 0) 4H ethyl) aniline p diazo N ZnOlz double salt.

(0 2H4O 4H N-methyl, N-(hydroxy di- CH3 ethoxyethyl) aniline p diazo CdClz double salt.

(C HaCHaO) H N-methyl-N-(hydroxy tet- 0 Ha raethoxyethyl) anilinep-diazo CdClz double N salt.

onlcngo n Prepared by similar reaction of 3 mols of ethylene oxide on 1 mol of N-dihydroxyethyl aniline followed by nitrosation or nitration, reduction of the nitroso or nitro group and diazotization of the amino group.

Prepared by similar reaction of 4 mols of ethylene oxide on 1 mol of N-dihydroxyethyl aniline followed by nitrosation or nitration, reduction of the nitroso or nitro group and diazotization of the amino group.

Prepared by similar reaction of 6 mols of ethylene oxide on 1 mol of N,N-dihydroxy ethyl aniline followed by nitrosation or nitration, reduction of the mtroso or nitro group and diazotization of the ammo group.

Prepared by similar reaction of 3 mols of ethylene oxide on 1 mol of N-methyl aniline followed by nitrosation or nitration, reduction of the nitroso or nitro group and diazotization of the amino group.

Prepared by similar reaction of 5 mols of ethylene oxide on 1 mol of N-methylaniline followed by nitrosation or nitration, reduction of the nitroso or nitro group and diazotization of the amino group.

The-formulas given 'for these diazos are the most probable ones. However, it is possible that theethylene oxideenters the'molecule in difierent ratios than indicated in the formulas thus forming isomers. For example, the formula for thediazo compound of Example 1 could be:

and that of the second diazo compound in the table could be:

)CH2CH2OMH N 20 CHzCHzOH while two additional isomers for the third compound. in r the table and three for the fourth compound readily suggest themselves.

We claim;

1. Diazotype photoprinting materials comprising a light sensitive diazo derivative of a p-phenylenediamine of the class having the formula:

wherein n and n are the same or different integers from 1-4 and an azo dye coupling component.

2. A diazotype photoprinting material comprising a light-sensitive diazo derivative prepared and an azo dye coupling component;

LA diazotype photoprinting material comprising a light-sensitive diazo derivative prepared from. an aromatic p-diamine, containing five ethylene oxide groups per molecule, of the probable formula:

and an azo dye coupling component.

CHaCHzOH )CHgCHnOhH N WILLIAM H. VDN GLAHN.

LESTER N. STANLEY.

GEORGE T. PARKER.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,217,189 Sus 0017. 8, 1940 2,280,722 Schneider et a1 Apr. 21, 1942 2,336,309 Snell et a1. Dec. 7, 1943 

1. DIAZOTYPE PHOTOPRINTING MATERIALS COMPRISING A LIGHT SENSITIVE DIAZO DERIVATIVE OF A P-PHENYLENEDIAMINE OF THE CLASS HAVING THE FORMULA: 